Method to monitor and control chemical treatment of petroleum, petrochemical and processes with on-line quartz crystal microbalance sensors

Abstract

Thickness-shear mode resonators which simultaneously measure mass deposition and fluid properties can be utilized to monitor petroleum processing, petrochemical and water treatment systems. Specialty chemical additive materials can be accurately and instantaneously added to control conditions detected by the thickness-shear mode resonators. The thickness-shear mode resonators are piezoelectric crystals used in conjunction with oscillator circuitry that can determine mass as well as viscosity and/or density of a fluid in contact with the piezoelectric surface.

Having thus described our invention, we claim: 
     
       1. A method for the rapid determination of a scaling, corrosion or biological growth condition occurring on a surface in contact with an industrial water contained in an industrial water system, and for taking steps to correct such condition which comprises the steps of: a. inserting a thickness-shear mode resonator device into the industrial water whereby the quartz surface of the thickness-shear mode resonator device is in contact with the industrial water;   b. continuously exciting the thickness-shear mode resonator device and measuring the output of the thickness-shear mode resonator device as the mass and viscosity-density components of the industrial water in contact with the thickness-shear mode resonator device;   c. continuously determining the condition of the industrial water contacting the quartz surface of the thickness-shear mode resonator device based on the mass and viscosity-density components of said industrial water; and then,   d. continuously correcting the condition of said industrial water in contact with the quartz surface of the thickness-shear mode resonator device by taking an action from the group consisting of: i. activating or deactivating a chemical feed pump applying a condition correcting chemical to the industrial water;   ii. increasing the flow of water out of the system; or,   iii. decreasing the flow of water out of the system.     
     
     
       2. The method of claim 1 wherein the industrial water system is a cooling tower. 
     
     
       3. The method of claim 1 wherein the condition monitored in the industrial water in contact with the quartz surface of the thickness-shear mode resonator device is biofouling, and the chemical feed pump adds a microbiocide or toxicant into the industrial water. 
     
     
       4. The method of claim 1 wherein the industrial water system is an industrial boiler. 
     
     
       5. The method of claim 1 wherein the condition of the industrial water monitored is selected from the group consisting of inorganic scaling, corrosion, and biofouling, and the chemical feed pump adds one or more treatment chemicals selected from the group consisting of water soluble scale inhibitors, biocides, and corrosion inhibitors. 
     
     
       6. The method of claim 1 wherein the quartz surface of the thickness-shear mode resonator device is mounted flush with the surface of the industrial water system through which the industrial water passes and the quartz surface of the thickness shear-mode resonator device is in contact with the industrial water. 
     
     
       7. The method of claim 1 wherein the quartz surface of the thickness-shear mode resonator device is inserted into the industrial water system on a temporary basis. 
     
     
       8. A method for the rapid determination of a fouling, corrosion, scale, or biological growth condition occurring on the surface of a hydrocarbon processing unit in contact with a hydrocarbon fluid and for taking steps to correct such condition which comprises the steps of: A. placing a thickness-shear mode resonator device into the fluid contained in the hydrocarbon processing unit whereby the quartz surface of the thickness-shear mode resonator device is in contact with the hydrocarbon;   B. continuously exciting the thickness-shear mode resonator device and measuring the output of the thickness shear-mode resonator device as the mass and viscosity-density components of the hydrocarbon fluid in contact with the thickness shear-mode resonator device;   C. continuously determining the condition of the hydrocarbon fluid contacting the quartz surface of the thickness-shear mode resonator based on the mass and viscosity-density components of said fluid; and then,   D. continuously correcting the condition of the hydrocarbon fluid contacting the quartz surface of the thickness-shear mode resonator by activating or deactivating a chemical feed pump applying a hydrocarbon fluid condition correcting chemical to the hydrocarbon processing unit.   
     
     
       9. The method of claim 8 wherein the hydrocarbon processing unit is a compressor, reboiler, heat exchanger, purification column, hold vessel, or reactor and the chemical feed pump applies a fouling inhibitor. 
     
     
       10. The method of claim 8 wherein the hydrocarbon processing unit is selected from the group consisting of hydrocarbon processing units producing alkenes and alkynes, and the chemical feed pump applies one of more ingredients from the group consisting of fouling inhibitors, corrosion inhibitors, and antifoams. 
     
     
       11. The method of claim 10 wherein the thickness-shear mode resonator device is placed on the surface of the hydrocarbon processing unit. 
     
     
       12. The method of claim 8 wherein the hydrocarbon processing unit is selected from the group consisting of hydrocarbon processing units producing styrene, acrylonitrile, acrylic acid, alkyl acrylates, vinyl chloride, butadiene, and isoprene. 
     
     
       13. The method of claim 12 wherein the thickness-shear mode resonator device is placed flush with the surface of the hydrocarbon processing unit and the quartz surface of the thickness-shear mode resonator device is in contact with the hydrocarbon fluid contained in the hydrocarbon processing unit. 
     
     
       14. The method of claim 8 wherein the hydrocarbon processing unit processes crude oil and the chemical feed pump applies one or more hydrocarbon fluid correcting chemicals from the group consisting of fouling inhibitors, corrosion inhibitors, scale inhibitors, and antifoams. 
     
     
       15. The method of claim 8 wherein the quartz surface of the thickness-shear mode resonator device is placed flush with the surface of the hydrocarbon processing unit and the quartz surface of the thickness-shear mode resonator device is in contact with the fluid contained in the hydrocarbon processing unit. 
     
     
       16. The method of claim 8 wherein the quartz surface of the thickness-shear mode resonator device contacts the fluid contained in the hydrocarbon processing unit on a temporary basis. 
     
     
       17. A method for the rapid determination of a viscosity-density or viscosity/temperature condition of a hydrocarbon fluid and for taking steps to correct or modify such condition which comprises the steps of: A. inserting a thickness-shear mode resonator device into the hydrocarbon fluid whereby the quartz surface of the thickness-shear mode resonator device is in contact with the hydrocarbon fluid;   B. continuously-exciting the thickness-shear mode resonator and measuring the output of said thickness shear-mode resonator device as the mass and viscosity-density components of the hydrocarbon fluid;   C. continuously determining the condition of the hydrocarbon fluid in contact with the quartz surface of the thickness-shear mode resonator based on the mass and viscosity-density components; and then,   D. continuously correcting the condition of the hydrocarbon fluid by activating or deactivating a chemical feed pump applying a condition correcting chemical to hydrocarbon fluid.   
     
     
       18. The method of claim 17 wherein the hydrocarbon fluid is contained in a container selected from the group consisting of a hydrocarbon processing unit, hydrocarbon storage tank, pipeline, or transport vessel. 
     
     
       19. The method of claim 18 wherein the thickness-shear mode resonator device is placed into the container holding such hydrocarbon fluid on a temporary basis. 
     
     
       20. The method of claim 18 wherein the thickness-shear mode resonator device is placed flush with the surface of the container holding such hydrocarbon fluid and the quartz surface of the thickness-shear mode resonator device is in contact with such hydrocarbon fluid. 
     
     
       21. A method for the rapid determination of the condition of a hydrocarbon/aqueous fluid mixture contained in a container, and for taking steps to correct or modify such condition which comprises the steps of: A. inserting into the hydrocarbon/aqueous fluid mixture at least one thickness-shear mode resonator device whereby the quartz surface of the thickness-shear mode resonator device is in contact with the hydrocarbon/aqueous fluid mixture;   B. continuously exciting the thickness-shear mode resonator device and measuring the output of the thickness shear-mode resonator as the mass and viscosity-density components of the hydrocarbon/aqueous fluid mixture;   C. continuously determining the condition of the hydrocarbon/aqueous fluid mixture based on the mass and viscosity-density components of said hydrocarbon/fluid mixture; and then,   D. continuously correcting the condition of the hydrocarbon/aqueous fluid mixture by activating or deactivating a chemical feed pump applying a condition correcting chemical to the hydrocarbon/aqueous fluid mixture.   
     
     
       22. The method of claim 21 wherein the hydrocarbon/aqueous fluid mixture is contained in a container selected from the group consisting of crude oil demulsification vessels, crude oil heater treaters, crude oil desalting units, ethylene quench water towers, dilution steam generating systems, hydrocarbon storage tanks, hydrocarbon transport vessels, waste water clarifiers, waste water treatment units, settling tanks, accumulators, and metal working fluid sumps. 
     
     
       23. The method of claim 22 wherein the quartz surface of the thickness-shear mode resonator device is inserted flush with the surface of the container containing such hydrocarbon/aqueous fluid mixture and the quartz surface of the thickness-shear mode resonator device is in contact with such hydrocarbon/aqueous fluid mixture. 
     
     
       24. The method of claim 22 wherein the quartz surface of the thickness-shear mode resonator device is inserted into the hydrocarbon/aqueous fluid mixture on a temporary basis. 
     
     
       25. The method of claim 21 wherein two or more thickness-shear mode resonator devices are utilized with at least one of such devices being positioned at a location to detect the presence of an aqueous phase and at least one of such devices being positioned at a location to detect the presence of a hydrocarbon phase.